Catalytic oxidation of light alkanes in presence of a base

Abstract

The presence of a base in the reaction mixture in a metal-ligand catalyzed partial oxidation of alkanes results in sustained catalyst activity, and in greater percent conversion as compared with oxidation in the absence of base, while maintaining satisfactory selectivity for the desired oxidation, for example the oxidation of isobutane to isobutanol.

The invention claimed is: 
     
       1. Method for partial oxidation of alkanes to alkanols which comprises contacting an alkane with a metal organic ligand catalyst in the presence of an inorganic base. 
     
     
       2. Method according to claim 1 wherein said metal is a transition metal. 
     
     
       3. Method according to claim 2 wherein said catalyst comprises a transition metal complex of a ligand selected from the group consisting of porphyrins, phthalocyanines, porphenes, porphycenes, 1,3-bis(arylimino)-isoindolines, acetates, Schiff bases, mono-, bi-, tri- and tetradentate systems, acetylacetonates, naphthenates, propanates, butyrates, benzoates, stearates, bipyridines, terpyridines, phenanthrolines, dithiocarbamates, xanthates, salicylaldimines, cyclam, dioxycyclams, pyrazoylborates, and tetraazamacrocycles. 
     
     
       4. Method according to claim 2 wherein said ligand is a porphyrin. 
     
     
       5. Method according to claim 4 wherein said porphyrin contains one or more electron-withdrawing atoms or groups in meso and/or beta positions. 
     
     
       6. Method according to claim 5 wherein said atoms or groups are selected from the group consisting of halogen, nitro, cyano, halocarbyl, nitrocarbyl and cyanocarbyl atoms or groups. 
     
     
       7. Method according to claim 6 wherein said ligand is a perhaloporphyrin. 
     
     
       8. Method according to claim 7 wherein said metal is selected from the group consisting of iron, cobalt, chromium, manganese, ruthenium and copper. 
     
     
       9. Method according to claim 8 wherein said metal is iron. 
     
     
       10. Method according to claim 2 wherein said ligand is a phthalocyanine. 
     
     
       11. Method according to claim 10 wherein said phthalocyanine contains one or more electron-withdrawing atoms or groups. 
     
     
       12. Method according to claim 11 wherein said atoms or groups are selected from the group consisting of halogen, nitro, cyano, halocarbyl, nitrocarbyl and cyanocarbyl atoms or groups. 
     
     
       13. Method according to claim 12 wherein said metal is selected from the group consisting of iron, cobalt, chromium, manganese, ruthenium and copper. 
     
     
       14. Method according to claim 2 wherein said ligand is acetylacetonate. 
     
     
       15. Method according to claim 14 wherein said metal is selected from the group consisting of iron, cobalt, chromium, manganese and ruthenium. 
     
     
       16. The method according to claim 15 wherein said metal comprises cobalt. 
     
     
       17. The method according to claim 15 wherein said metal comprises ruthenium. 
     
     
       18. Method according to claim 1 wherein said base is an alkali metal compound. 
     
     
       19. Method according to claim 18 wherein said alkali metal is sodium. 
     
     
       20. Method according to claim 18 wherein said alkali metal is potassium. 
     
     
       21. Method according to claim 1 wherein said base is an alkaline earth metal compound. 
     
     
       22. Method according to claim 21 wherein said alkaline earth meal is calcium. 
     
     
       23. Method according to claim 1 wherein said base is a basic ion exchange resin. 
     
     
       24. Method according to claim 1 wherein said alkane is isobutane. 
     
     
       25. Method according to claim 1 wherein the strength of said base is equivalent to about 2 to about 12 normal sodium hydroxide. 
     
     
       26. Method according to claim 25 wherein said strength is equivalent to about 6 to about 10 normal sodium hydroxide. 
     
     
       27. Method according to claim 1 wherein the amount of said base is in the range from about 1 to about 9 parts by weight per 100 parts by weight of said alkane. 
     
     
       28. Method according to claim 27 wherein said amount is in the range from about 3 to about 7 parts by weight per 100 parts by weight of said alkane.